Process for breaking petroleum emulsions employing certain oxyalkylated 3, 3&#39;-iminobispropylamines



May 14, 1957 w. .1. DICKSON 2,792,373

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATED 3,5'- IMINOBISPROPYLAMINES Filed Sept. 15, 1954 BINARY REACTION PRODUCT FOR OXYETHYLATION 3,3'- IMINOBISPRQOPYLAMINE Cc DD I00 BINARY REACTION PRODUCT FOR OXYPROPYLATION I INVENTOR PROCESS FGR BREAKING PETROLEUM EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED 3,3'-OBISPROPYLAMINES Woodrow J. Dickson, Monterey Park, Calit'z, assignor to Petrolite Corporation, Wilmington, Deb, a corporation of Delaware Application September 15, 1954, Serial No. 456,297

7 20 Claims. (Cl. 252-344) This invention relates to processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities particularly inorganic salts, from pipeline oil.

More specifically then, the present invention is concerned with a process for breaking petroleum emulsions employing a dimulsifier including a cogeneric mixture of a homologous series of glycol ethers of 3,3'-iminobispropylamine. The cogeneric mixture is derived exclusively from 3,3'-iminobispropylamine, propylene oxide and ethylene oxide in such weight proportions so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum 3,3 -iminobispropylamine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines connecting A, B, F, E. Our preference by far is to use the compositions which represent less than one-half of this total area, to wit, the smaller trapezoid A, B, D, C.

It is immaterial as to whether one reacts the amine with propylene oxide first and then with ethylene oxide, or with ethylene oxide and then with propylene oxide; or, for that matter, one may employ a mixture of the two oxides; or, if desired, one may add a small amount of ethylene oxide, then propylene oxide, and then more ethylene oxide.

Referring to the hereto attached drawing it is simplified by noting that one may react 3,3-iminobispropylamine with enough ethylene oxide so the binary reaction product falls within the mixture identified by the line CCDD on the extremity of the graph which shows combinations derived solely from 3,3'-iminobispropylamine and ethylene oxide. After obtaining such binary reaction product it can then be reacted with propylene oxide so as to bring it within the area of the trapezoid A, B, F, E, or preferably within the smaller trapezoid A, B, D, C.

Similarly, one can produce a binary reaction product from 3,3'-iminobispropylamine and propylene oxide as identified by the comparable line AA-BB and subject this reaction product to oxyethylation so as to bring the 2,792,373 Patented May 14, 1957 composition within the area of the trapezoid and preferably within the area of the small trapezoid A, B, D, C.

For the purpose of resolving petroleum emulsions of the water-in-oil type, I prefer to employ oxyalkylated derivatives, which are obtained by the use of monoepoxides, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

The above mentioned test, i. e., a conventional emulsification test, simply means that the preferred product for demulsification is soluble in a solvent having hydrophobe properties or in an oxygenated water insoluble solvent, or even in a mixture containing a fraction of a water-soluble oxygenated hydrocarbon solvent, and that when shaken with water the product may remain in the nonaqueous solvent or, for that matter, it may pass into the aqueous solvent. In other words although it is xylene soluble, for example, it may also be water soluble to an equal or greater degree.

For purpose of convenience, what is said hereinafter will be divided into three parts:

Part 1 is concerned with the oxyalkylation of 3,3- iminobispropylamine in a general way;

Part 2 is concerned with the oxyalkylation of 3,3- iminobispropylamine using two different oxides, i. e., propylene oxide and ethylene oxide so as to produce derivatives falling within said compositional limits as previously described and noted hereinafter in detail;

Part 3 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds.

PART 1 The oxyalkylation of amines is Well known. This applies particularly to reactions involving monoepoxides having not over 4 carbon atoms, such as ethylene oxide and propylene oxide. As to the oxyalkylation of a monoamine such as cyclohexylamine, see U. S. Patent No. 2,626,922, dated January 27, 1953, to De Groote. As to the oxyalkylation of a polyamine, see U. S. Patents Nos. 2,552,530, 2,552,531 and 2,552,534, all dated May 15, 1951, and all to De Groote.

The oxyalkylation of an amine is comparable to other well known oxyalkylations and under certain conditions may require variation. There is no problem if the amine is a liquid or if it is xylene-soluble or soluble in an equivalent solvent, or can be melted and reacted at the melting point. This happens to be the case when one is employing 3,3'-iminobispropylamine. Actually theprocedure in effect is no different if one had an insoluble solid and in such instance one of the most satisfactory procedures is to use a slurry of the finely powdered material in xylene comparable to the oxyalkylation of sorbitol. As to this procedure, see Example A in U. S. Patent No. 2,552,528, dater May 15, 1951, to De Groote.

The oxyalkylation of 3,3-iminobispropylamine may be considered comparable to the oxyalkylation of a liquid such as triethanolamine. Needless to say, such compound or any comparable liquid can be subjected to oxyalkylation in absence of a solvent or vehicle. However, in the initial exhaustive oxyalkylation of any product it is usually desirable to use a minimum amount of the product so that considerable oxide can be added. This presents the diificulty of getting effective stirring at the early stages. For this reason it is convenient to add an inert solvent such as xylene or a high boiling petroleum solvent, without differentiating whether one obtains a solua salt. This is-not true where earths-are used which act 'as as -'caustic soda,

tion or a slurry, or in the case of a liquid, a suspension or temporary emulsion. In the present instance the product as such is a liquid and soluble in any one of a number of suitable solvents but, in any event in due course oxyalkylations of the kind herein described produce products which are soluble in either xylene or high boiling aromatic petroleum. For this reason what is said hereinafter in regard to oxyalkylation becomes comparatively simple and is comparable to that of any other liquid reactant which can be mixed readily with an inert solvent.

In order to illustrate why the herein contemplated compounds or said products are co'generic mixtures and not single chemical compounds, and why they must be described in terms of manufacture, and molal ratio or percentage ratio of reactants, reference is made to a monohydric alcohol. 'ss mmmiis ropyramine has 5 reactive hydrogen atoms and thus at the beginning or early stage of "oxyalkylation may have as m'a'iiy asks reactive hydrogen atoms attached to either nitrogen *or oxygen. Thus, 'for the present purpose it ma be considered the same as an amino alcohol having 5-hydroxy1 radicals. However, for the moment one can forget whether the hydrogen atoms are attached to nitrogen or to oxygen and for that matter the plurality 'of reactive hydrogen atoms and simply consider what happens when a monohydric alcohol is's'ubjectedtooxyalkylation.

If one selects any 'hyd'roxyl'ated compound and subjects such compound to ox-yalkylation, such as; oxyethylation or oxypropylation, it becomes obvious-that one is really producing a polymer of the alkylene oxide "except for the terminal group. This is particularly true'where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a-compound is subjected to ox-yethylation so as =to'intro'du'c'e 30 units of ethylene oxide, his well known that one does not obtain a single constituent which, for sakeof convenience, may be indicated as RO(C2H4O)30H. Instead,

I one obtains a co'generic mixture of closely related 'h'omologous compounds in which the formula may be shown as the following: RO(C2H4O)'1iH, wherein n, as far as the statistical average goes, is 30, but the individual-members present in significant amount may vary from instances where n has a value of 25 and perhaps less, to a point where n may represent 35 or more. Such mix ture is, as stated, a cogenericclosely 'relatedseries of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Bolymerization, by Paul J. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed'out byFlory and other investigators, there is no satisfactory method, based on either experimental or mathematical examination, of indicating the exactproportion of the various members of touching homologous series which appear incogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difiiculty, it is necessary to resort to some other metl'iodof description.

What has been said in regard to a monohydric compound of course is multiplied many times in the case of 'a compound such as 3,3'-irninobispropylamine.

Although acid catalysts are used in 'oxyalkylations they are used to a lesser extent in the oxyal-kylat ions of basic amines and the like. Under'such circumstances one'may have to use enough of the acidic-catalyst 'to neutralize the basicity of the-product and convert into certain clays or prepared acidic "catalysts. In any use basic catalysts 'such sodium 'rnethylate, "or the like.

event, it is 'rnypreference to :si'on or asa solution.

'wasallowed to rise to 4 PART 2 extensive as in the present instance, one requires acatalyst after the initial stage and it is just as simple to add it from the very beginning.

The oxypropylation of a polyarnine, such as 3,3-i.minobispropylamine, is comparatively simple because such products or similar products are usually liquids atordinary temperature and invariably at oxyalkylation temp'eratu're's. Indeed, the procedure is simply .to oxyalkylate without addition of any catalyst if desired and then when oxyalkylation slows up add the usual basic catalyst, such as powdered caustic soda or powderedsodiurn methylate. If desired, such catalyst can be added at the very beginning. It is also desirable in such cases where exh'austive oxyalkylation is concerned "toad'd a diluent, such as xylene, high boiling petroleum solvent, or the like, at the very beginning. Such solvents usually are miscible but if not miscible one obtains a suspension or temporary emulsion and as soon as oxyalkylation has proceeded'to even aslight degree the entire mass is homogeneous. I

"Specific reference is made to the instant application which is concerned with ethylene oxide and propylene oxide or the equivalents. Actually, whether One 'us'e's ethylene oxide or propylene oxide or, for 'that matter, butylene oxide, one preferably starts with a polyamine suspended in the form of aslurry, an emulsion, a suspen- There would be a slurry in event the amine is a solid and insoluble. In the present case, however, the. amine is a liquid'as' pointed out.

If desired, one can employ an alkylene carbonate, such as ethylene carbonate, butylene carbonate, or propylene carbonate, for the initial oxyalkylation. Where such initial oxyalkylation has gone far enough to convert the polyamine into a solvent-soluble product, i. e., soluble in xylene or an aromatic petroleum solvent, one can then use the oxides. The carbonates, of course, cost more than the oxides'and there is no real advantage inmost case's unless one starts with an insoluble amine such 'as'tris- (hydroxymethyl) aminomethanea'ndthis does not apply in the present case.

, In any event, as is wellkno'wn'the' oxyethylation of'poly- "amines proceeds as readily 'as the oxypropylation, and

Example lad I The reaction .vessel'employed was a-sta'inless:steel autoclave with the usual devices for heating, heat control, stirrer, inlet, outlet, etc., Which'is conventional in this type of apparatus. The capacity was approximately 4 liters. The-stirrer was operated at a speed "of approximately 250 R. P. M. There were charged'into theautoclave SOO-grams of 3,3'iminobispropylamine, 300grams of xylene, and-15-grams of sodium methylate. The autowith nitrogen gas :and stirring startedimmediately and heat applied. The temperature approximately C. At this particular time the addition of propylene oxide was started. Propylene oxide was added continuously at such speed that it was absorbed by the reaction as added. The amount added in this operation was 1500 grams. The

in xylene was employed in connection with ethylene oxide and the same mixture on a percentage basis was obtained as in the above examples where propylene oxide and 3,3- iminobispropylamine were used.

time required to add the propylene oxide was 2% hours. In i g f g g fg ggg D this eriod the temperature was maintained at and t ent 11.66 no 0 i P o 4 h th The two oxldes can be mixed together 1n suitable pro- 150 using coohng Waiter throilg 6 portions and subsequently subjected to joint oxyalkylation mner C0115 when neceisary and Otherwls? applymg h so as to obtain products coming within the specified limits. if q The maxlmum Pressure dfmng the reaction 10 In such instances, of course, the oxyalkylation may be was 48 POunds P Square inch- Ignonng the xylehe and described as random oxyalkylation insofar that one can- Sodium methylate and considering only the 3,3"1min0 not determine the exact location of the propylene oxide hispfepylamihe eehvehiehee, the resultant Product or ethylene oxide groups. In such instances the prorepresents 3 Parts y Weight Of P py oxide o One cedure again is identically the same as previously de- P y Weight of P Pylamine. The xylene scribed and, as a matter of fact, I have used such methods present represented approximately .6 part by weight. in connection with 3,3'-iminobispropylamine.

Actually, 3,3-iminobispropylamine at times may con- Example tain a trace of moisture. My preference is to prepare The reaction mass of Example laa was tran ferred to the slury with an excess of xylene and distill off a part a larger autoclave (capacity 15 liters). Without adding of the xylene so as to remove any trace of water and then any more solvent or any more xylene the procedure was flush out the mass with nitrogen. Even so, there may be a repeated so as to add another 1500 grams of propylene few tenths of a percent of moisture remaining although at oxide under substantially the same operating conditions times examination indicates at the most it is merely a but requiring about 3% hours for the addition. At the r end of this step the ratio represented approximately 6 pfevleusly P h out h slmplest P P e of to 1 (ratio propylene oxide to 3,3-iminobispropylamine). h to P R a blhal'y reaetleh Product Of bispropylamine and ethylene oxide on the one hand or Example 3,3'-iminobispropylamine and propylene oxide on the In a third step, instead of adding 1500 grams of propyl- Other hand, f e with the ether fi Note line. one oxide to the product of Example laa, 1625 grams CCDD whfeh lhdleeies h h hlllary feaetleh were added. The reaction slowed up and required ap- Product obiamed from 3,3 'lmmobl,spropylamme and proximately 6 hours, using the same operating tempera ethylene Gxlde one P approxutlately 66'6% to tures and pressures. The ratio at the end of the third step 22 fy i a allld fipproxlmately to 9.25 arts by weight of propylene oxide per weight 3 o Immo lspropy ammfa' was 35 Similarly, 1f one refers to the line AABB 1t means 015343 'lmmoblspropylamme' one would employ from 1.95% of 3,3'-iminobispropyl- Example 4aa amine up to 14.3% of 3,'-iminobispropylamine and At the end of the third step (Example 3aa) the autog i 'z of Propylene omde up to 98'05% of propyl Cleve was Opened and an additional 5 grams of sodmm 4 In other operations I have proceeded to do as follows: methylate added, the autoclaveflushed out as before, and Mixed QR 33' iminobispmpy1amine with an aromatic the fourth and final oxyalkylation completed, using 1625 petroleum Solvent and with powdered caustic soda I grams of Propylehe Oxlde, and the oxyalkylanon was have stirred this mixture at 125 to 130 C. for a short complete Within 31/2 hours using the same temperature period of time, approximately one-half hour, flushed out range and Pressure as previously- At the end of the with nitrogen, and then subjected to vacuum so as to eetioh the P h represented approximately Parts eliminate any moisture. I then started to oxypropylate Propylene oxlde by Welght to one P of 3,3"1mm0 and continued until oxypropylation was complete and b1spropylam1ne. then immediately followed with ethylene oxide. In these IjIavmg Obtained YP RY P 'PY examples the amount of materials used are indicated in amlhe the preduefs were suhleeied t0 q y t a pounds, and in each instance, of course, a suitable size maflflel Comparable to the eXyethyleheh 01 methanol" autoclave was used. Although the oxyalkylation started am r for that Thai-tel} 111 the Same y that Y- under vacuum the maximum pressure at any time was P py e e Subjected to exyethyletieh in the about 10 to 15 pounds. An efficient agitating device manner (lfiSCilbCd 111 U. S. Patent NO. 2,652,394, dated was used and stirring speed was approximately September 15, 1953.101}; Gfoeie- Indeed, the Procedure R. P. M. These data covering nine oxyalkylations are is p f y Simple the reason that One is Wofkincluded in Table I, immediately following. The time ing WiT-h a hquid and also that ethylene oxide is more periods are shown. Incidentally, I have repeated these reactive than Propylene OXide- AS result, using the same operations using ethylene oxide first and then same amount of catalyst one can oxyethylate more rapidly propylene oxid and I have al o mixed the two oxides and usually at a lower pressure. and completed the same nine oxyalkylations under sub- The same procedure using 3,3-iminobispropylamine stantially the same conditions.

TABLE I High- 3,-iminoboiling Caustic Propylene Ethylene Time, Temp. Maximum Ex. Nos. bispropylaromatic soda, lbs. oxide, lbs. oxide, hrs. C. press., lbs

armne, lbs. petroleum lbs. per sq. in.

solvent, lbs.

.Refefrring. again to the, ratio of the initial reactants basedon the trapezoid in, attached drawing, Ihavecalcus lated the percentage of the three initialreactants'fpr the points A, B, C, D,-E, and F, and Nos. 1 through 14, inclusive. I have also calculated initial binary mixtures corresponding in essence. to the lines CC-DD and AABB, all of which appears in self-explanatory form in Table II, immediately following.

' The products obtained by" the above procedure usually show some color varying from alight arnberto-a pale straw. They can be-bleached in the usual fashion using bleaching clays, charcoal or an organic bleach, sueh'as peroxide or peracetic acid, or the like.

Thereare :certainwariants :which can be employed without detractingiromthe metes and boundsof the invention, but for all practical purposesthere is nothing to TABLE II 'Iertiary-mixturapercent basis Binary intermediate mixtures, percent basis Points on boundary 3,3'-imino- Propy- 'Ethy- 3,3'-imino- Propy- 3,3'-imino- Ethyof area bispropyllene lene ,bispropyllene bispropyllene 81111119 oxide oxide 7 amine oxide amine oxide 1.75 "88.26 '10. 1. 95 98.05 14. 9 85. 1 1. 75 5O. 0 48. 25 3.138 96. 62 3. 5 96. 5 5 O 75. 0 20.0 6. 24 93. 76 20. 0 80. 0 5.0 55.0 40. 0 8. 32 91. 68 11. 1 88.9 10. O 70.0 20. 0; g '12. 5 87. 5 33. 4 '66. 6 10.0 60.0 30. 0 14. 3 85. 7 25. 0 75. 0 4. 72 76. 4 18. 88 5. 8 94. 2 20. 0 "80. 0 3. 62 78. 3 18. 1 4. 42 95. 58 13. 1 -86. 9 3. 07 66. 3 30. 63 4. 43 95. 57 9. 1 90. 9 2. 84 83.0 14.16 3. 51 96. 49 16. 7 83. 3 2. 66 57. 5 39. 84 4. 42 95. 58 6. 93. 75 2. 48 g 72. 6 24. 92 3. 3 96. 7 9.04 90. 96 2. 21 '64. 7 33.09 3. 3 96. 7 '6. 26 93:74 2.16 81. 5 16.54 2. 58 97. 42 11. 55 88. 45 1. 97 74.5 23. 53 2. 58 97. 42 7. 73 92. 27 4. 0 61. 0 35. 0 6. 17 93.83 10. 28 89. 72 1. 8 83. 0 16. 0 2. 12 97. 88 10. l 89. 9 7. 0 70. 0 23. 0 9. 1 89. 9 23. 76. 65 8. 0 57. 0 '35. 0 l2. 3 87. 7' 18. 6 81. 4 9.0 65.0 26. 0 12. 15 87.85 25. 7 74.3

As previously pointed out, the oxyalkylation of 3,3- iminobispropylamine or similar hydroxylatedmonoor polyamineshas been describedin the literature and is described-also in detail above. All one need do is employ such conventional oxyalkylation procedure to obtain productscorresponding to the compositions as defined. Attention is again directed to the fact that one need not add the entire amount of either oxide at one time but that a small portion of one could be added and then another small portion of the other, and the process repeated.

For purposeof illustration I have prepared examples in three. different Ways corresponding to the compositions on the drawing. In the first series propylene oxide and ethylene oxide were mixed; this series is indicated as Aa,-Ba, etc., through and-including 14a; in the second series propylene oxide was used first followed by ethylene oxide and this series is indicated as Ab, Bc, etc., through andincluding 14b; and finally in a third series, ethylene oxide was used first followed by propylene oxide and this series is indicated as Ac, Bc, etc., through and including 140. This relationship .isshown in Table III.

1 TABLE III Composition Composition Composition where oxides where propylwhere ethyl- Composition corresponding aremixed enc oxide eue oxide to following point prior to oxyused first {01- used first to]- alkylation lowed by ethlowed by proylene oxide 1 pylene oxide Aa Ab Ac Ba Bb Bc Ca Cb Cc Du Db Dc Ea Eb Ec Fa I Fb Fc (in 6b 6c 13a "13b 13c be gainedby such variants and the result is merely increased" cost. For -instance,- any one of the two oxides can be replaced toaminor percentage and'usually to a very small degree, by oxide which would introduce substantially the same group along with a side chain, for instance, one could employ glycidyl methyl ether, glycidyl ethyl 'ether,--glycidyl isopropyl ether, glycidyl butyl ether or the like.

Increased branching also may beeifected by the use of an imine instead of a 'glycide, or a methyl glycide. Thus one can use ethylene imine, or propylene imine in the same way described for glycide or methyl glycide. An additional efiect is obtained due to the basicity of the nitrogen atom. The same thing is true as far as the inclusion of nitrogen atoms if one uses a compound of the kind previously described such as a dialkylaminoepoxypropane. ;Excellent products are obtained byrreacting 3,3'eiminobispropylamine with one to .5 moles of ethylene imine; and then; proceeding in the same manner herein described.

Inthe hereto appended claims reference has been made to glycol ethers of 3,3 -iminobispropylamine. Actually it well may be that the products should be'referred to as polyol ethers of 3,3-iminobispropylamine in order to emphasize the fact-that the final products of reaction have more than two hydroxyl'radicals. However, the products may be considered asrhypothetically derived by reaction of 3,3-iminobispropylamine with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols. For this reason there seems to be a preference to use the terminology glycol ethers of 3,3'-iminobispropylamine.

In a trapezoid such as A, B, D, C, the area can be .divided conveniently into five portions by first drawing (drawing .on a. larger scale and in dotted lines only. In

- the trapezoid refers to the area defined by the middle rectangle. The area of one rectangle is defined'by being between the upper apex and the center rectangle, and the other by being between the lower apex and the center rectangle, all of which is perfectly plain by reference to the drawing. An attempt to draw additional lines and to number them in the same trapezoid A, B, D, C, would only tend towards confusion and thus the present means is being employed to point out the various areas which, in turn, appear in the sub-generic claims hereto appended. Thus in the drawing, the area designated V corresponds to the area within the upper triangle, the area W corresponds to the area within the lower triangle, the area X corresponds to that of the middle rectangle, and the areas Y and Z correspond to those of the other rectangles.

PART 3 As to the use of conventional demulsifying agents, reference is made to U. S. Patent No. 2,626,929, dated January 27, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and eifect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 512 herein described.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent, is

1. A process for breaking petroleum emulsions of the water-in-oil type chracterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of 3,3'-iminobispropylamine; said cogeneric mixture being derived exclusively from 3,3',iminobispropylamine, propylene oxide and ethylene oxide in such weight proportion so the average composition of said cogeneric mixture stated in terms of the initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum 3,3'-iminobispropylamine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines A, B, F, E.

2. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that at least part of the propylene oxide is added first.

4. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that all the propylene oxide is added first.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of 3,3- iminobispropylamine; said cogeneric mixture being derived exclusively from 3,3'-iminobispropylamine, propylene oxide and ethylene oxide in such weight proportion so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum 3,3'-iminobispropylamine content is at least 1.75% and which trapezoid is identified by the fact that its area lies within the straight lines A, B, D, C; with the proviso that all the propylene oxide is added first in the presence of an alkaline catalyst.

6. The process of claim 5 with the proviso that the reactant composition approximates a point in the area corresponding with V within the upper apex of the trapezoid A, B, D, C.

7. The; process of claim 5 with theg'proviso that; the I reactant composition approximates a point in the area corresponding with W within the lower apex of the trapezoid A, B, D, C.

8. Theprocess of claim 5 with the proviso that the reactant composition approximates a point in the area corresponding with X of the central part of the trapezoid A, B, D, C.

9. The process of claim 5 with the proviso that the reactant composition approximates a point in the area corresponding with Y between the central part of the trapezoid A, B, C, D, and the upper apex.

10. The process of claim 5 with the proviso that. the reactant composition approximates a point in the area corresponding with Z between the centnal part of the trapezoid A, B, D, C, and the lower apex.

11. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of 3,3'-iminobispropylamine; said cogeneric mixture being derived exclusively from 3,3-iminobispropylamine, propylene oxide and ethylene oxide in such weight proportion so the average composition of said cogeneric mixture stated in terms of the initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum 3,3-iminobispropylamine content is at least 1.75 and which trapezoid is identified by the fact that its area lies within the straight lines A, B, F, E; with the proviso that the hydrophile properties of said cogeneric mixture is an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

12. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

13. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that at least part of the propylene oxide is added first.

14. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that all the propylene oxide is added first.

15. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of 3,3- iminobispropylamine; said cogeneric mixture being derived exclusively from 3,3'-iminobispropylamine, propylene oxide and ethylene oxide in such weight proportion so the average composition of said cogeneric mixture stated in terms of initial reactants lies approximately within the trapezoid of the accompanying drawing in which the minimum 3,3'iminobispropylamine content is at least 1.75 and which trapezoid is identified by the fact that its area lies within the straight lines A, B, D,

C; with the proviso that all the propylene oxide is added first in the presence of an alkaline catalyst; with the proviso that the hydrophile properties of said cogeneric mixture in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

16. The process of claim 15 with the proviso that the reactant composition approximates a point in the area corresponding with V within the upper apex of the trapezoid A, B, D, C.

17. The process of claim 15 with the proviso that the reactant composition approximates a point in the area corresponding with W within the lower apex of the trapezoid A, B, D, C.

18. The process of claim 15 with the proviso that the reactant composition approximates a point in the area corresponding with X of the central part of the trapezoid A, B, D, C.

19. The process of claim 15 with the proviso that the reactant composition approximates a point in the area References Cited in the: file of this' -patent UNITED STATES PATENTS Bondet a1; Dec, 281.1948 De Groote May 15,1951 De Groote May 15;". 195 1 Monson Mar. 11,1952 Ferrero et 'al.- Dec. 16,1952 Huscher-et a1 Aug. 18;1953- 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF 3,3''-IMINOBISPROPYLAMINE; SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM 3,3''-IMINOBISPROPYLAMINE, PROPYLENE OXIDE AND ETHYLENE OXIDE IN SUCH WEIGHT PROPORTION SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF THE INITIAL REACTANTS LIES APPROXIMATELY WITHIN THE TRAPEZOID OF THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM 3,3''-IMINOBISPROPYLAMINE CONTENT IS AT LEAST 1.75% AND WHICH TRAPEZOID IS IDENTIFIED BY THE FACT THAT ITS AREA LIES WITHIN THE STRAIGHT LINES A,B,F,E. 